Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage

Abstract Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C−O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod) 2 ] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C−N bond cleavage in the presence of a [Pd(PPh 3 ) 2 Cl 2 ] catalyst. These methods enable selective sequential functionalizations of arenes having both C−N and C−O bonds in one pot.